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3,044,865
United States A Patent Oflice
Patented July 17, 1962
2
1
such liquids as water and various organic liquids such as
3,044,865
kerosene, acetone, benzene, toluene, xylene, and other
.
METl-l?l) 0F CONTROLLING PLANT GRGWTH BY
Tim APPLICATTON 0F 3-HALO-2,3-DIHYDRO
petroleum distillate fractions or mixtures thereof.’ When
liquid formulations are employed, or dry materials pre
pared which are to be used'in liquid form, it is desirable
in certain instances additionally to employ a wetting,
emulsifying or dispersing agent to facilitate use of the
THTQPHENE-Ll-DIOXIDE
Trying Rosen, Painesville, Ohio, assignor to Diamond
Ailiali Company, Cievelziand, Ohio, a corporation of
Delaware
No Drawing. Filed Feb. 13, 1959, Ser. No. ‘702,947
6 Claims. (on. 71-25)
formulation, e.g., Triton X-—155 (alkyl aryl polyether
alcohol).
This invention relates to the novel compounds 3-chloro
pletely understand the present invention and the preferred
In order that those skilled in the art may more com
and 3-fluoro-2,3-dihydrothiophene-1,1-dioxides, their prep
methods by which the same may be carried into effect,
the following speci?c examples are offered:
aration and utilization.
This is a continuation-in-part of applicatoin Serial No.
EXAMPLE I
606,972, Rosen, ?led August 30, 1956, now Patent No. 15
Preparation of 3-Chl0ro-2,3-Dihydrothiophene-1,1-‘
2,928,766.
The novel compounds of this invention have the
formula
Dioxide
There is added dropwise 1.06 gm. (0.01 mol) of sodium
20 carbonate in 15 ml. of water to a warm solution (80° C.)
of 3.78 gm. (0.02 mol) of 3,4-dichlorotetrahydrothio
phene-l,1-dioxide in 50 ml. of water. After the addition
is completed, the mixture is heated under re?ux for one
s
02
hour and then cooled. ,Coolingof the reaction mixture
Thus, it will be understood that the compounds of this 25 and ?ltering yields a white crystalline solid melting at
wherein X is chlorine or fluorine.
invention are as follows:
.l24°-128° C. which is unreacted starting material. The
mother liquid is concentrated and cooled 'to obtain a
yellow oil which is extracted with chloroform and reduced
in volume to obtain yellow oil which crystallizes on stand
.
3-chloro-2,3-dihydrothiophene-l, l-dioxide
30 ing. a This solid is recrystallized from carbon tetrachloride
and colorless needlelike crystals melting at 82° C. are
isolated.
'
‘
Chemical analysis of the product indicates that the
. desired 3-chloro-2,3-dihydrothiophene~l,l-dioxide
35
is obtained, the following analytical results being reported
1n terms of percent by weight.
40
02
Element -
The presently preferred S-chloro compound can con
veniently be prepared by dehydrochlorination of 3,4-di
70..
chlorotetrahydrothiophene-1,l-dioxide in an aqueous me
H.
dium, preferably alkaline, e.g., rendered alkaline by so 45
I Calculated
Found
I 31.50
’
_
01
31.45
3.30
3.33
23. 25
24.2
dium carbonate or calcium carbonate. The reaction may
be carried out at varying temperatures although generally
The pure compound was distilled and'found to boil at
heating is desirable, a typically practicable temperature
164° C. at 10 mm. Hg.
being about 100° C. The 3-ftuoro-dihydrotetrahydrothio
phene-1,1-dioxide can be prepared by reacting 3-chloro 50
EXAMPLE’ II
2,3-dihydrothiophene-l,l-dioxide with hydrogen ?uoride.
it has been found that 3-chloro or ?uoro-2,3-dihydro
thiophene-l,l-dioxides exhibit a high degree of biological
activity and are especially useful as active ingredients in
various applications where biological activity is required,
e.g., in the ?eld of parasiticides, e.g., nematocides, and in
the ?eld of plant growth regulants, e.g., herbicides, and
Preparation of 3-1?‘lu0ro-2,3-Dihydrothiophene-J ,1 ,
Dioxidev
.
.
Into a reactor comprising a polyethylene bottle are
placed 63 gms. (0.49 mol) of silver ?uoride and 30.4
.gms. (0.2 mol) ‘of 3-chloro-2,3-dihydrothiophene-1,l-di
(oxide. The bottle, containing a calcium chloride drying
tube, is placed in a dish containing Dry Ice and acetone.
Hydrogen ?uoride from a gas cylinder is condensed'in the
The compounds of this, invention exhibit biological
activity as will be set forth in some detail hereinafter in 60 bottle. About 100 ml. of hydrogen ?uoride is collected.
The bottle is. then placed in an ice bath andleft at room
the speci?c examples and may be employed in a variety
temperature for several hours. The hydrogen ?uoride is
of formulations, both liquid and solid, including ?nely
evaporated and the resultant solid extracted With chlorof
divided powders, granular materials, as Well as various
the like.
_
form. This extraction is repeated, the chloroform being
liquid solutions, concentrates, emulsi?able concentrates,
slurries, and the like, depending upon the application in 65 evaporated and 19 gms. of crude material recovered, com
tended and the formulation media employed. It will be
appreciated that compounds of this invention form excel
lent biologically active ingredients which may be employed
as an essential ingredient in various compositions which
prising a 70% yield based on the 3,4-dichlorotetrahydro
thiophene-1,1-dioxide employed. The brown solid is re
crystallized twice from benzene to obtainaproduct melt;
ing at 67—69° C. The product contains no chlorine as
may include such diluents, extenders, ?llers, conditioners, 70 shown by sodium fusion. The material is further recrys—
solvents, and the like, as various clays, diatomaceous
earth, talc, spent catalyst, alumina-silica materials and
tallized'from chloroform to obtain a pure White material
melting at 68-69° C. Production of the desiredyf‘com-i
3,044,865
4
pound (SFO2C.,H5) is indicated by the following elemen
tal analysis:
plied in amounts of 16, 8 and 4 lbs. per acre. The esti
mated percentage stands, as compared to checks and other
responses on broadleaf and grass at the foregoing concen
Element
Percent
calculated
35. 30
3. 68
14. 00
Percent
actual
35. 39
3. 82
12. 40
trations are (broadleaf) 5, 10, 75 and (grass) 30, 100 and
100, respectively. This data indicates a high degree of
toxicity with respect to germinating seed in the soil espe
cially against broadleaf plants.
EXAMPLE IX
An alternative preparation of 3-chloro-2,3-clihydrothio
An LR. reference curve indicates the presence of 10
phene-1,l-dioxide is as follows:
a-C=C- and an S02 group.
In a 4-liter beaker containing 2 liters of water at 90° C.
EXAMPLE III
there are dissolved 250 gm. (1.32 mol) of 3,4-dichloro
tetrahydrothiophene-l,l-dioxide and 92.5 gm. (0.925 mol)
Experiments are conducted utilizing 3-chloro-2,3-dihy
drothiophene-l,1-dioxide by pouring 51 m1. portions of a 15 of calcium carbonate. The aqueous reaction mixture is
2000 parts per million aqueous formulation of this com
pound prepared using 5% acetone as a solvent and 0.01%
Triton X—155 as an emulsi?er into 4-inch clay pots on
allowed to cool and is ?ltered to yield a solid product
which is extracted with 250 ml. of hot benzene. The
benzene extract is cooled and ?ltered. The resultant
?ltrate, after removal of further solids deposited, is con
soil in which tomato or bean plants are growing. The
thus-treated plants are held in a greenhouse for 10 days 20 centrated to a volume of about 100 ml. and cooled.
The cooled ?ltrate is then extracted with 2—500 ml.
and are examined and rated in accordance with a phy
portions and 4-250 ml. portions of chloroform. The re
totoxicity rating scale ranging from 0=no injury to a
sultant chloroform solution is then washed with 250 ml.
value of 11, meaning the plant is killed. Using such a
of water. The remainder of the solvent is separated to
procedure, the tomato plants are killed. The same pro
cedure indicates a phytotoxicity value rating of 10 25 yield a dark residue which slowly crystallizes. This
crystalline product is dissolved in 150 ml. of hot benzene,
against bean plants indicating a high degree of herbicidal
allowed to cool to room temperature and stand for 4
action.
hours to effect precipitation of a solid and is then ?ltered.
EXAMPLE IV
This ?ltrate is evaporated to a volume of about 75 ml.
Further to illustrate biological activity 3-chloro-2,3-di 30 and is ?ltered to obtain the desired 3-chloro-2,3-dihydro
hydrothiophene-l,l-dioxide is evaluated as a nematocide
against the root knot nematode (Meloidogyne sp). In
this experiment, one-half gallon glazed crooks of soil in
fested with 3-5 gm. of knotted tomato roots are treated,
thiophene-l,l-dioxide.
EXAMPLE X
Using the general procedure of Example III, 3-?uoro
at the rate of 128 lbs. per acre, by mixing 3-chloro-2,3 35 2,3-dihydrothiophene-1,1-dioxide has a phytotoxicity rat
dihydrothiophene-l,l-dioxide with the soil. The results
ing of 11, thus indicating plant kill, against tomato and
of such tests, using a rating from 0 for no infestation to
bean plants when applied at 128 lbs. per acre. Further
5 for severe infestation, indicate that the 3-ch1oro—2,3-di
tests both via foliage spray (6400 ppm.) and via soil
hydrothiophene-l,1-dioxide produces a 0 rating on the
watering (128 lbs. per acre) indicate kill of tomato and
tomato plants while an untreated check sample has a rat 40 bean in both instances. The foliage spray test also kills
corn under similar conditions.
ing of 4.7, indicating an extremely high concentration of
nematodes.
'
EXAMPLE V
A further nematocidal test is made using 3-chloro-2,3
dihydrothiophene-1,1-dioxide against the non-plant para
sitic nematode, Panagrellus redivivus, by exposing the
nematodes to the chemical in small watch glasses (27
mm. diam. x 8 mm. deep) within a 9 cm. Petri dish for
24 hours. A test formulation comprising test chemical,
5% acetone, 0.01% Triton X—155, and the balance water,
is used. The percentage mortality at concentrations of
EXAMPLE XI
Using the procedure of Example X, 3-?uoro~2,3-dihy
drothiophene-l,l-dioxide, at 64 lbs. per acre, a zero
growth rating with respect both to broadleaf and grass
plants, indicates a high degree of herbicidal activity. A
post-emergent foliage spray test against tomato, bean
and oats indicates a rating of 11, 11 and 10, respectively,
thus
demonstrating herbicidal action in post-emergent
50
application also.
spectively, thus indicating a high degree of nematocidal
effectiveness.
'
EXAMPLE XII
2000 and 1000 parts per million are 100% and 72%, re
Using the procedure of Example V, 3-?uoro-2,3-dihy
drothiophene-Ll-dioxide exhibits a 100% nematode kill
EXAMPLE VI
55 in contact action at 1000 ppm.
nematodes in soil at concentration of 64, 32 and 16 lbs.
It is to be understood that although the invention has
been described with speci?c reference to particular em
bodiments thereof, it is not to be so limited, since changes
per acre. In this test no phytotoxicity is noted and nem
and alterations therein may be made which are within
A further experiment is conducted using 3-chloro-2,3
dihydrothiophene-l,l-dioxide against tomato root knot
atode infection ratings of 0.0, 0.5 and 1.3, respectively, are 60 the full intended scope of this invention as de?ned by the
obtained as compared to an untreated check sample in
appended claims.
What is claimed is:
1. The method of controlling plant growth which com
EXAMPLE VII
prises applying to said plant a herbicidally effective
A further nematocidal test is conducted by applying 65 amount of a composition of matter containing as an es
3-chloro-2,3-dihydrothiophene-1,1-dioxide via direct mix
sential active ingredient a 3-halo-2,3~dil1ydrothiophene
ing with soil as a nematocide against root-knot nema
1,1-dioxide.
todes using tomato as the indicator plant at concentrations
2. The method of controlling plant growth which com
of 32, 24 and 16 lbs."per acre. The nematode infection
prises applying to seeds of said plant a herbicidally effec
ratings resulting are 0.0, 0.0 and 0.2, respectively, as 70 tive amount of a composition of matter containing as an
against an untreated check sample nematode rating of
essential active ingredient a 3-halo-2,3-dihydrothiophene
festa‘tion of 4.8.
>
infection of 5.0. g
l,lrdioxide.
EXAMPLE VIH
A herbicidal test is conducted using 3-chloro-2,3-dihy
3. The method of controlling plant growth which com
prises applying to the soil around said plant growth a
drothiophene-l,1-dioxide as a pre~emergent herbicide ap
75 herbicidally e?ective amount of a composition of matter
3,044,865
5v
‘
-
~
>
containing as an essential active ingredient a 3-ha1o-2,3dihydrothionhene-l,l-dioxide-
_
References Cited in the ?le of this patent
-
UNITED STATES PATENTS
4. The method of controllinv plant growth which com
prises
‘
applying ‘ to said
..
plan? a herbicidally
- effective_
amount of a composition of matter contalnmg as an 68 5
mgredlent a 3aware-2,3-d1hydr0thwphene-
,
,
2,898,205
2,939,871
gzleg?sneftafl'
. ________
““““““__
"oliib'zg’
.
,
Pyne ________________ __ Aug 4, 1959
Pym et aL __________ __ June 7, 1960
5. The method of controlling plant growth which com-
prises applying to said plant a'herbicidally e?ective
FOREIGN PATENTS
'
'
amount of a composition of matter containing as an es- 10
542,599
Belglum —————————— -—'-- NOV- 30, 1955
sential active ingredient a 3~?uoro-2,3-dihydrothiophene-
536,564
Canada ------------- --_Jan- 29, 1957
1,1-dioxide.
'
>
6. The method of controlling plant growth which comOTHER REFERENCES
prises applying to the soil around said plant growth a
Bailey et al.: Journal American Chemical Society, vol.
herbicidally effective amount of a composition of matter 15 76, PP- 1932-1936 (1953).
containing as an essential active ingredient a 3_-chloro~2,3Kfllg 8t 31'? Journal Of Organic Chemistry, VOL 23, PP
dihydrothiophene-l,l-dioxide.
212-215 (1958).